Internally cross-linked wrinkled fibrous silica nanocomposite by bipyridinum dichloride

bridge: an efficient catalyst in the synthesis of α,β-unsaturated diketones

Seham Nasseri, Ali Reza Kiasat*

Chemistry Department, College of Science, Shahid Chamran University of Ahvaz,

Ahvaz, Iran

[email protected]
Abstract

In this research, we designed a novel internally cross-linked wrinkled fibrous organo-silica nanocomposite

containing bivalent organic cationic bridges in the framework. For this gold, bivalent organosilane bridging agent,

Si(OEt)3-BiPy+22Cl--Si(OEt)3 was easily prepared through nucleophilic substitution reaction of (3-chloropropyl)

triethoxysilane and bipyridine. In the next step, silanated bivalent cationic bipyridinium dichloride bridge was

introduced into the pore walls of dendritic fibrous nanostructured silica through a sol−gel process under open-vessel

reflux conditions. The obtained heterogeneous hybrid nanocomposite, KCC-1-Bipy+22Cl-, was characterized by FT-

IR, EDX, TGA, and FE-SEM. The rationale was that such wrinkled fibrous, due to its abundant pores and slits,

would acts as nanoreactor and would be an excellent catalyst in organic transformation due to the presence of

quaternary ammonium units into the pore walls. Owing to the fact that the α-β-unsaturated carbonyl compounds can

further be used in the synthesis of valuable intermediates, the catalytic ability of the nanocomposite was tested in the

C=C bond formation reaction via Knoevenagel condensation of aldehyde and active methylene compounds under

solvent free conditions. In addition to convenience, utilization of the catalyst with high catalytic activity and good

reusability, makes this method as an interesting option for facile and efficient synthesis of α,β-unsaturated diketones

derivatives.

KEYWORDS

KCC-1; KCC-1-Bipy+22Cl-; Wrinkled Fibrous Silica; Organic-inorganic hybrid silica framework; Organic cationic

bridges; Knovenagel Condensation; α,β-unsaturated diketones

Introduction

Fibrous silica nanospheres (KCC-1) as an excellent mesoporous silica with unique open three-dimensional dendritic

superstructure has received considerable attention in recent years. KCC-1 that also well-known as dendritic fibrous

nanosilica (DFNS) has a high surface area that is due to its fibrous morphology and not to pores. Therefore, most of

its internal surface area is accessible for guest materials, provides unusually high activity in catalysis. In addition, it

has been widely accepted as an ideal candidate for carrier various nanomedical material owing to its high specific

surface area, good biocompatibility, low toxicity, fibrous morphology, good thermal/hydrothermal properties, high

mechanical stability and easy surface modification, which has been extensively used in numerous fundamental

research and practical applications [1-3]. The amorphous nature of the concentric fibers of KCC-1 and the

abundance of surface silanol groups lead to a hydrophilic surface and low its catalytic activity. There are several
methods to improve the hydrophobicity, including introducing framework organic segments and silylation of surface

silanol groups [4,5].

The C-C bond formation is a crucial reaction for producing various highly functionalized complex molecules such

as biologically active compounds. In the past, the Knoevenagel reaction entailed a big part of these reactions via

condensation reaction between activated methylene and carbonyl compounds which promoted by nitrogen-based

catalysts. In recent years, a large number of catalytic systems were developed for this reaction. In addition, the

Knoevenagel reaction in heterogeneous media has also been reported in the presence of alumina, silica, zinc and

magnesium oxides, ionic liquids, tertiary amines, TiCl 4, ZnCl2, LaCl3, organometallic catalysts and other catalysts

[6-8]. However, even for the most favorable systems, the reaction often suffers from expensive catalysts, long

reaction times, laborious work-up procedures, and use of organic solvents or toxic metals. Hence, there is an

existing need for developing efficient and new methods based on green chemistry to improve the Knoevenagel

condensation reaction [8].

By having these facts in mind and continues of our interest in the preparation of organic −inorganic hybrid silica

framework [4,5], now we wish to report preparation of internally cross-linked wrinkled fibrous silica nanocomposite

by bipyridine dichloride bridges in the pore walls, KCC-1-Bipy+22Cl-, through a sol-gel process under open-vessel

conditions. The catalytic efficiency of the nanocomposite was also tested in the C=C bond formation reaction of

carbonyl compounds and active methylene compounds via Knoevenagel under solvent free conditions.

Experimental

Reagents and Material

All chemical materials including urea, cyclohexane, n- pentanol, (3-cholopropyl) triethoxysilane,

cetyltrimethylammonium bromide (CTAB) and tetra ethylorthosilicate (TEOS), Bipyridine, 1,3-dictones, aromatic

aldehydes and solvents were purchased from Merck and Fluka companies and used without further purification.

Products were characterized by comparison of their physical data, such as IR spectra were recorded on a (St-jean

Baptist Ave Bomem 450 (400-4000 Cm-1) Series 1998 FT-IR spectrometer (PerkinElmer) and Melting points were

measured by Thermo Scientific. The purity determination of the products and reaction monitoring were

accomplished by TLC on silica gel PolyGram SILG/UV 254 plates. The particle size and external morphology of

the nanocomposite particles were characterized by field emission microscope scanning electron microscopy, FE-

SEM (MIRA3-LMU), scanning electron microscopy, SEM (Philips XL30). Transmission electron microscopy,

TEM (Zeiss-EM10C-100 kV instrument).

Preparation of silanated bivalent cationic bipyridinium dichloride bridge, Si(OEt)3-BiPy+22Cl--Si(OEt)3

To a solution of 1.2 g of 4,4- Bipyridine (7.7 mmol) in toluene (20 ml), 3.7 g of (3-chloropropyl)triethoxysilane

(15.4 mmol) was added and stirred for 72h under inert argon atmosphere at 90 °C. The obtained brown solid was

centrifuged and washed three times with ethanol. Finally, Si(OEt) 3-BiPy+22Cl--Si(OEt)3 was dried in a vacuum oven

for 3h at 80 °C.

General procedure for the synthesis of organic−inorganic hybrid silica framework based on the dendritic

fibrous silica, KCC-1-Bipy+22Cl-

1 g of CTAB (2.7 mmol) was dissolved in 30 mL of an aqueous solution of urea which containing 0.6 g of urea (10

mmol). The solution was stirred for 15 min at room temperature and marked with "A". Then, n-pentanol (1.5 ml)

was dispersed in cyclohexane (30 ml) and the oily solution was poured into the aqueous solution A and stirred

vigorously. This mixture was marked with "B".

Afterwards, 1 g of TEOS (5 mmol) and 1 g of organo-silica precursor , Si(OEt)3- BiPy+22Cl--Si(OEt)3 (1.6 mmol)

were mixed together and placed in the ultrasonic for 10 min and added dropwise to the "B" until a cloudy emulsion

obtained. The reaction mixture was stirred vigorously for 30 min at room temperature and then heated for 24 h at 75

°C. The produced nanocomposite, KCC-1-Bipy+22Cl-, was centrifuged and washed with deionized water and

ethanol. Subsequently, KCC-1-Bipy+22Cl- was dispersed in acidic ethanol and heated for 24 h at 70 °C to remove

any remaining CTAB. The brownish solid was dried in a vacuum oven at 80 °C for 12 h.

General procedure for the synthesis of KCC-1

To a solution of 0.2 g of CTAB (0.54 mmol) in deionized water (10 ml) 0.24 g of urea (0.004 mmol) was added and

stirred for 30 min at room temperature and labeled as solution A. Then, in the step 2, 0.47 g of TEOS (2.3 mmol)

was poured into cyclohexane (10 ml) and stirred at room temperature until obtained an oily homogenous solution.

This was labeled as solution B. In the step 3, in the round bottom flask, solution A was dropwise added to the oily

solution B and stirred for 1h at room temperature. The mixture was labeled as C.

Finally, n- pentanol (0.6 ml) was added dropwise to the solution C and stirred 30 min at room temperature until a

mixed cloudy emulsion is obtained. Afterwards, the mixture was refluxed for 21h at 80 °C. After that, the reaction

mixture was cooled to ambient temperature and obtained white solid was centrifuged and washed three times with

deionized water and ethanol. At the end, the white solid was calcined for 6h at 550 °C to remove the remaining

CTAB.

General Procedure for the synthesis of α, β-unsaturated diketones promoted with KCC-1-Bipy+22Cl-

To a mixture of an active methylene compound (dimedone /1,3-dimethylbarbituric acid/thiobarbituric acid/indandion)

(1 mmol) and substituted benzaldehyde (1 mmol), KCC-Bipy +22Cl- (4 mg) was added and stirred at 80°C under

solvent-free condition. The progress of the reaction was monitored by TLC (n-Hexane: ethyl acetate (4:1)). After
completion of the reaction, a mixture of hot DMSO (1ml) and ethanol (2ml) was added to the mixture and stirred

vigorously. Then, the nanocomposite was separated by filtration and washed with hot ethanol. After cooling of the

mixture to room temperature, 10 ml of distilled water was dropwise added to it and the precipitated product was

filtered and dried under vacuum at 80°C. Therefore, the product was purified by recrystallization in ethanol.

Results and discussion

The synthetic schematic outline for the preparation of internally cross-linked wrinkled fibrous silica nanocomposite

by bipyridinum dichloride bridges was sketched in Scheme 1. For the synthesis of the organic-inorganic hybrid

silica framework based on the dendritic fibrous silica, KCC-1-Bipy+22Cl-, in the first step the silanated bivalent

cationic bipyridinium dichloride was easily prepared through nucleophilic substitution reaction of (3-chloropropyl)

triethoxysilane and bipyridine under reflux conditions. In the next step, Si(OEt)3-BiPy+22Cl--Si(OEt)3 bridge was

introduced into the pore walls of dendritic fibrous nanostructured silica through a sol−gel process under open-vessel

reflux conditions. In this synthesis process, TEOS and Si(OEt)3-BiPy+22Cl--Si(OEt)3 were used as silica source,

CTAB as template and structure-directing agent, cyclohexane as co-solvent, n-pentanol as co-surfactant for

stabilizing the micelles/microemulsion droplets, and urea as hydrolyzing agent.

 Step I
Cl- Si(OEt)3
N N
N
+
(EtO)3Si(CH2)3Cl
Toluene/ Argon atm.
90 oC, 3 days (EtO)3Si +
N
Cl-

Si(OEt)3-BiPy+2 2Cl- -Si(OEt)3

Step II

Stir/r.t / 10 min
CTAB + Urea (aq) Solution A
Stir
Solution B
poured into A
Stir/r.t
CH3(CH2)3CH2OH + Cyclohexane

Step III

Ultrasonic/ 10 min Solution B

Si(OEt)3-BiPy+2 2Cl- -Si(OEt)3 + TEOS

1. Stir/ r.t/ 30 min

2.stir/ 75 oC/ 24h

KCC-BiPy+2 2Cl-

Scheme 1 General approach for the preparation of internally cross-linked wrinkled fibrous silica nanocomposite by
.bipyridinum dichloride bridge

To qualitatively determine the incorporation of bipyridinum dichloride unites into the pore walls of KCC-1, The FT-

IR spectra of KCC-1, Si(OEt)3-BiPy+22Cl--Si(OEt)3, and KCC-Bipy+22Cl- nanocomposites were recorded and shown

in Fig. 1. In the both FTIR spectra of KCC-1 and KCC-bipy+22Cl-, the Si−O−Si symmetric and asymmetric

stretching vibrations at 805 cm –1and 1090 cm–1were observed (Fig.1). The C−H stretching of aromatic and aliphatic

moieties at 2900−3040 cm−1 and a weak symmetric deformation of CH2 observed at 1470 cm−1 in the KCC-

bipy+22Cl- and Si(OEt)3-BiPy+22Cl--Si(OEt)3 spectra indicate that the bipyridinum dichloride unites were
successfully introduced into the pore. It was also confirmed by the presence of characteristic absorption bands for

C=C and C=N at 1600 cm−1and 1645 cm−1, respectively.

.Fig. 1 FT-IR spectra of the KCC-1 (a) Si(OEt)3-BiPy+22Cl--Si(OEt)3 (b), KCC-biPy+22Cl- (c)

Also to confirm the incorporation of bivalent cationic bipyridinium dichloride bridge into the pore walls of dendritic

fibrous nanostructured silica, KCC-bipy+22Cl- was analyzed by Energy-Dispersive Spectroscopy (Fig. 2). EDX

confirmed the presence of Si, O, C and N in the nanocomposite.

.Fig. 2 The EDX spectrum of KCC-bipy+22Cl- nanocomosite

The elemental mapping analysis of KCC-bipy+22Cl- is shown in Fig. 3. According to the mapping photographs, N,

C, Si, O, and Cl were uniformly dispersed in the structure of nanocomposite, indicating that the organic bridges

were homogeneously incorporated into the pore walls of KCC-bipy+22Cl-.

 .-Fig. 3 The elemental mapping of KCC-Bipy+22Cl

The thermal behavior of KCC-bipy+22Cl- was measured by Thermo-Gravimetric Analysis and shown in Fig. 4. A

significant decrease in the weight percentage of the KCC-bipy+22Cl- at about 130 °C is related to desorption of water

molecules from the nanocomposite surface (6 %). In addition, a series of weight loss appears at 267, 385, 508 and

700 °C, which can be attributed to the decomposion of organic parts. Therefore, the quantitative estimation of the

amount of organic unites in the structure of nanocomposite is about 37.88% .

.-Fig. 4 TGA-DTG diagram of KCC-bipy+22Cl

By the field emission scanning electron microscopy, morphology, and particles size of KCC-1 and KCC-bipy+22Cl-

were confirmed. As can be seen in Fig. 5, FE-SEM photographs of KCC-1 (Fig. 5a-c), show the spheres with

needle-shaped structure and average diameters about 250 nm. The FE-SEM images of KCC-Bipy+22Cl-

nanocomposite clearly indicates that bivalent cationic bipyridinium dichloride bridge was introduced into the pore

walls of dendritic fibrous nanostructured silica without any changes in the morphology of KCC-1 (Fig. 5d-f). As

shown in Fig. 5, by introduction of cationic organic units in the KCC-1 structure, the average diameters was

reduced.

.Fig. 5 FE-SEM of KCC-1(a-c), KCC-1-Bipy+22Cl- (d-f)

After confirming the structure of the KCC-bipy +22Cl-, it was decided to investigate its catalytic activity in the facile

synthesis of some α,β-unsaturated compounds via Knoevenagel condensation reaction under environmentally benign

conditions (Scheme 2).

Scheme 2 C=C bond formation reaction of substituted benzaldehyde and active methylene compounds via
Knoevenagel promoted by KCC-1-Bipy+22Cl-.

Initially, the synthesis of 2-(4-chloro-benzylidene)-5,5-dimethyl-cyclohexane-1,3-dione was selected to optimize the

best reaction conditions. The reaction was carried out by heating a mixture of p-chlorobenzaldehyde (1mmol) and

dimedone (1mmol) in the presence of various amounts of KCC-1-Bipy +22Cl- and different reaction conditions. As

shown in Table 1, the shortest time and best yield are achieved in the presence of 0.004g of catalyst at 80°C and

under solvent free conditions (Table 1, Entry 4).

It should be noted that although the condensation reaction is also performed in ethanol (Table 1, Entry 8), it cannot

be a good choice compared to the solvent-free conditions. In addition, to investigate catalytic effect of bivalent

cationic bipyridinium dichloride unites in the pore walls of KCC-1-Bipy+22Cl-, the same reaction was tested in the

presence of KCC-1. As shown in Table 1, even after longer time (Entry 10), the reaction was not complete.
 Table 1 Optimization reaction conditions

Conditions
Entry Catalyst (mg) Solvent/Tem.(οC)/Time Yield
(min)
1 No catalyst Sf/80 οC/ 60 No Reaction

2 KCC-1-Bipy+22Cl- (0.002 g) Sf/80 οC/ 20 No Reaction

3 KCC-1-Bipy+22Cl- (0.003 g) Sf/80 οC/ 20 In completed

4 KCC-1-Bipy+22Cl- (0.004 g) Sf/80 οC/ 10 99%

5 KCC-1-Bipy+22Cl- (0.004 g) Sf/r.t./ 60 No Reaction

6 KCC-1-Bipy+22Cl- (0.004 g) Sf/60 οC/ 60 In completed

7 KCC-1-Bipy+22Cl- (0.004 g) n-hexane/ Reflux/ 60 In completed

8 KCC-1-Bipy+22Cl- (0.004 g) EtOH/ Reflux/ 60 80%

9 KCC-1-Bipy+22Cl- (0.004 g) H2O/ Reflux/ 60 In completed

10 KCC-1 (0.004 g) Sf/80 οC/ 60 In completed

Sf: Solvent free

After optimizing the reaction conditions, to study the scope and generality of the introduced methodology in the

synthesis of titled compounds, a wide range of aromatic aldehydes derivatives bearing both electron-donating and

electron-withdrawing groups were successfully condensed with variety of active methylene compounds such as

dimedone, indandione, 1,3- dimethyl barbituric acid and thiobarbituric acid to produce the corresponding α,β-

unsaturated compounds in good to excellent isolated yield and in short reaction time (Scheme 3, Table 2).
 Scheme 3 Knoevenagel condensation reaction of various aromatic aldehydes with 1,3-diketones in the presence of
the KCC-1-Bipy+22Cl-.

Table 2 Knoevenagel condensation reaction of various aromatic aldehydes and 1,3-dicetones in the presence of the
KCC-1-Bipy+22Cl- under solvent free reaction conditions

H O H O H O
H O

CH3
CH3 CH3 CH3 O
O Cl O O CH3
CH3 CH3 CH3 NO2
2'a 2'b OMe
2'd
2'c
Time: 20 min, Yield: 60% Time: 10 min, Yield: 99 %
Time: 15 min, Yield: 99 % Time: 10 min, Yield: 95 %
mp: (183-185) mp: (150-152) mp: (198-200)
mp: (183-185)
mp (reported): [190-192] mp (reported): [125-127]
mp (reported):[187-190] [10] mp (reported): [202-204]
[9] [9] [10]
H O
H O O H Cl O H

CH3 H3CN H3CN

MeO O CH3
CH3 O2N O O N O O N O Cl
2'e CH3 CH3 CH3

Time: 20 min, Yield: 80% 2'f 3'a 3'b

mp: (117-120) Time: 80 min, Yield: 72% Time: 10 min, Yield: 70% Time: 60 min, Yield: 90%
mp (reported): [127-129] mp: (185-187) mp: (150-155) mp: ( 155-158)
mp (reported): [185-187] mp (reported): [152-155] mp (reported): [154-156]
[11] [10] [12] [11]
O H NO2 O H O H O H

OMe
H3CN H3CN H3CN H3CN

O N O NO2 O N O OMe
O N O CH3 CH3 O N O
CH3 CH3

3'c 3'd 3'e 3'f

Time: 30 min, Yield: 90% Time: 40 min, Yield: 99% Time: 20 min, Yield: 99% Time: 10 min, Yield: 60%
mp: (157-160 ) mp: (180-182) mp: (159-162) mp: (135-139)
mp (reported): [159-161] mp (reported): [190-193] mp (reported): [174-177] [13] mp (reported): [133-134]
[15] [14] [12]
 O H O H Cl O H O H

H3CN HN HN HN

O N O OH S N O S N O Cl S N O Me
CH3 H H H
3'g 4'a 4'b 4'c
Time: 20 min, Yield: 99% Time: 10 min, Yield: 99% Time: 35 min, Yield: 90% Time: 20 min, Yield: 99%
mp: (285-289) mp: (235-240) mp: 390 d mp: (320-325)
mp (reported): [297-298] mp (reported): [234-236] mp (reported): mp > 300 mp (reported): mp > 300
[11] [17] [17] [16]
O H O H O H O H NO2

HN HN HN HN

S N O OMe S N O N(Me)2 S N O OH S N O
H H H H
4'd 4'e 4'f 4'g
Time: 35 min, Yield: 99% Time: 25 min, Yield: 99% Time: 35 min, Yield: 99% Time: 40 min, Yield: 90%
mp: (325-330 ) mp: (290-292) mp: (345-350) mp: (210-215)
mp (reported): mp > 300 mp (reported): mp ≥300 mp (reported): mp > 300 mp (reported): [246-247]
[17] [16] [16] [17]
H O
H O H O O

O
Cl O OMe MeO O
O
5'b 5'c 5'd
5'a
Time: 5 min, Yield: 95% Time: 5 min, Yield: 98% Time: 5 min, Yield: 80%
Time: 10 min, Yield: 80%
mp: (178-179) mp: (112-115) mp: (151-155)
mp: (143-147)
mp (reported): [178] [18] mp (reported): [139-141] mp (reported): [159] [18]
mp (reported): [150] [18]
[19]
H O
H O
H O OH H O

Me O

(Me)2N O O
O 5'h
5'e OH Time: 5 min, Yield: 92%
5'f 5'g
Time: 5 min, Yield: 53% mp: (145-150)
Time: 5 min, Yield: 73% Time: 5 min, Yield: 76%
mp: (203-205) mp (reported):[148-149]
mp: (200-204) mp: (214-216)
mp (reported): [205] [18] mp (reported): [196] [21] mp (reported): [221] [21] [20]

H O H O
OH H O H O
MeO

H2 N O NC O
O HO
5'j O
5'i 5'k
Time: 5 min, Yield: 95% Time: 5 min, Yield: 95% 5'l
Time: 5 min, Yield: 95% Time: 5 min, Yield: 52%
mp: (255-258) mp: (215-220)
mp: (202-205) mp: (212-214)
mp (reported): [261-262] mp (reported): [233-234]
mp (reported): [225] [21] mp (reported): [215] [21]
[20] [20]
H O H O

O O2N O
NO2
5'm 5'n
Time: 5 min, Yield: 92% Time: 5 min, Yield: 95%
mp: (251-252) mp: (228-230)
mp (reported): [251-252] mp (reported): [230-232]
[18] [18]
The acceleration effect of the KCC-1-Bipy+22Cl- in the synthesis of α,β-unsaturated compounds can probably be

explaine based on the these facts that:

* The pore walls containing bivalent cationic bipyridinium dichloride unites in nanocomposite can be act as a

reaction vessel and increase the possibility of effective collision of starting materials via create the suitable

environment.

* The carbonyl group of the aldehyde protonate by hydroxyl surface of KCC-1-Bipy+22Cl-which causes the carbon

of the aldehyde group to become more electron positive.

* The nanocomposite accelerates deprotonation of active methylene group of diketone by hydrogen bonding and

following it Cl anion abstract a hydrogen from the active methylene and form a carbanion.

Table 3, shows the comparison between the catalytic efficiency of KCC-1-Bipy+22Cl- and other catalyst reported in

the literature. From these results, it is clear that this internally cross-linked wrinkled fibrous silica nanocomposite in

comparison with other catalyst provided excellent yields in shorter time and under green conditions.

Table 3 Comparison of efficiency of the present method in the Knoevenagel condensation reaction of 4-
chlorobenzaldehyde and dimedone with previous reports methods.
Reaction Condition
Time (min)/Tem
Entry Catalyst Yield (%) Ref
(℃)/Solvent

1 Piperidine 60 min/ reflux/ EtOH 80 [9]

2 [PEG(mim)2][OH]2 180 min / r.t/ H2O 88 [22]

3 Ni-nanoparticles 60 min/ r.t./ EtOH 81 [23]

2-hydroxyethylammonium
4 30 min/ r.t./ Ionic Liquid 63 [24]
formate
IV- DES (deep eutectic solvents
5 10 min/ r.t./Ionic Liquid 92 [25]
based on CeCl3.7H2O with urea)
6 KCC-1-Bipy+2 2Cl- 10 min/80℃/ Solvent Free 99 Present

One of the most important aspects in the field of catalyst is the possibility of recycling and reusing it. Accordingly,

the ability to reuse the nanocomposite in the Knoevenagel condensation reaction of 4- chlorobenzaldehyde and

dimedone was tested. For this propose, after reaction completion, the catalyst separated by simple filtration, washing

with ethanol, drying at 80 0C under vacuum and reused in next run. As shown in Fig. 6, nonocomposite can be

recycled at least five times with no noticeable loss in its activity.

 100 99
98
96
96 95
94

% Yield
92
90 90
90
88
86
84
1 2 3 4 5

Run

Fig. 6 Reusability of the KCC-1-Bipy+22Cl-.

The FT-IR spectra of the reused catalyst for five runs is shown in Fig. 7. This image is confirmed the high stability

of the reused nanocatalyst after five runs.

Fig. 7 FT-IR spectra of the reused catalyst after five runs.

Conclusion

In summary, KCC-1-Bipy+22Cl- as a novel internally cross-linked wrinkled fibrous organo-silica nanocomposite

containing bivalent organic cationic bridges in the framework was easily prepared through sol−gel process under

open-vessel reflux conditions. The catalytic ability of the nanocomposite was proved in the C=C bond formation

reaction via Knoevenagel condensation of aromatic aldehyde and active methylene compounds (dimedone,
indandione, 1,3- dimethyl barbituric acid and thiobarbituric acid ) under solvent free conditions. In addition to

convenience, utilization of the catalyst with high catalytic activity and good reusability, makes this method as an

interesting option for the facile and efficient synthesis of α,β-unsaturated diketones derivatives and therefore offers

economic and environmental benefits.

Author contributions In this study, A.R. kiasat designed the study. S. Nasseri performed all experiments. All

authors evaluated the results and prepared the manuscript.

Declarations

Conflict of interest The authors declare that they have no conflict of interest.

Proclamation of generative artificial intelligence and artificial intelligence-assisted technologies in the writing

process.

During the preparation of this work, the author(s) did not use any artificial intelligence and take full responsibility

for the content of the publication.

Acknowledgements

We gratefully acknowledge the support of this work by Shahid Chamran University Research Council (Grant No.

SCU.SC98.88).

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